Showing 1–50 of 63 results for author: Zurek, E

Anharmonicity and Nonadiabaticity in Hydride Superconductors

Authors: Shashi B. Mishra, Francesco Belli, Eva Zurek, Elena R. Margine

Abstract: We study superconductivity in representative hydrides using anharmonic phonons, electron-phonon vertex corrections, and full-bandwidth Eliashberg theory. The high-pressure binary hydrides H3S, YH6, and YH9 must be treated with both anharmonic and nonadiabatic corrections, whereas the ambient-pressure PdH/PdD/PdT series is strongly anharmonic but remains adiabatic, reproducing the inverse isotope e… ▽ More We study superconductivity in representative hydrides using anharmonic phonons, electron-phonon vertex corrections, and full-bandwidth Eliashberg theory. The high-pressure binary hydrides H3S, YH6, and YH9 must be treated with both anharmonic and nonadiabatic corrections, whereas the ambient-pressure PdH/PdD/PdT series is strongly anharmonic but remains adiabatic, reproducing the inverse isotope effect without sizable vertex contributions. LaBeH8 exhibits weak anharmonicity, while vertex corrections reduce the critical temperature (Tc) by approximately 4 K, leaving the predicted Tc above experiment. To identify when treatments beyond harmonic, adiabatic Migdal-Eliashberg theory are required, we introduce the anharmonic renormalization $A_λ$ and the vertex ratio $R_{V}$ as material-specific diagnostics. △ Less

Submitted 14 August, 2026; originally announced August 2026.

Comments: 21 pages, 15 figures

Geometry-Based Neural-Network Prediction of Electron Localization Function Topology in Dense Hydrogen

Authors: Xiaoyu Wang, Miriam Marqués, Sergio Gómez, Francesc Serratosa, Eva Zurek, Julia Contreras-García

Abstract: We develop a machine-learning framework to predict the electron localization function (ELF) of pure, dense hydrogen directly from atomic geometry, bypassing explicit electronic-structure calculations. Trained on first-principles data spanning multiple pressure regimes in dense fluid hydrogen, the model achieves high accuracy ($R^2 > 0.99$) and faithfully reproduces the global distribution of the E… ▽ More We develop a machine-learning framework to predict the electron localization function (ELF) of pure, dense hydrogen directly from atomic geometry, bypassing explicit electronic-structure calculations. Trained on first-principles data spanning multiple pressure regimes in dense fluid hydrogen, the model achieves high accuracy ($R^2 > 0.99$) and faithfully reproduces the global distribution of the ELF. A combined real- and reciprocal-space analysis reveals that the residual error is dominated by smooth, long-wavelength components with correlation lengths exceeding typical H--H bonding scales, and that the magnitude of these components increases systematically with pressure. Despite being trained exclusively on dense fluid hydrogen networks, the model transfers robustly to crystalline hydrogen configurations, preserving key features of ELF topology, including critical points and hydrogen-network connectivity. Taken together, these results suggest a viable route toward geometry-based, high-throughput evaluation of hydrogen-networking characteristics in both fluid and crystalline hydrogen. △ Less

Submitted 29 April, 2026; originally announced April 2026.

Journal ref: Chemistry - A European Journal 0 (2026) e00030

Metal Atom (Dis)Order and Superconductivity in YCaH$_{n}$ ($n=8-20$) High-Pressure Superhydrides

Authors: Masashi W. Kimura, Seong Won Jang, Nisha Geng, Eva Zurek

Abstract: High-pressure superhydrides have attracted much attention due to their high superconducting critical temperatures ($T_\text{c}$s). Herein, density functional theory (DFT) calculations are used to study the structures and properties, including potential for metal atom disorder and doping-enhanced $T_\text{c}$, within Y-Ca superhydrides with YCaH$_{n}$ ($n=8-20$) compositions. For YCaH$_8$ numerous… ▽ More High-pressure superhydrides have attracted much attention due to their high superconducting critical temperatures ($T_\text{c}$s). Herein, density functional theory (DFT) calculations are used to study the structures and properties, including potential for metal atom disorder and doping-enhanced $T_\text{c}$, within Y-Ca superhydrides with YCaH$_{n}$ ($n=8-20$) compositions. For YCaH$_8$ numerous phases that differed in the arrangement of the metal atoms were found to be nearly isoenthalpic, suggesting the importance of configurational entropy on stability. The equimolar ratio of the two metal atoms brought the Fermi level to a peak in the density of states, enhancing $T_\text{c}$ to 149~K and 170~K for $P4/mmm$ and $Cmmm$ YCaH$_{8}$, respectively, at 180~GPa within the isotropic Eliashberg formalism. YCaH$_{12}$ was also predicted to be disordered, however the $T_\text{c}$s of the ordered variants spanned a wide range from 105-253~K at 200~GPa, showing that doping could either mildly enhance or drastically reduce $T_\text{c}$ from that of the parent compounds. For YCaH$_{18}$ and YCaH$_{20}$, only a single dynamically stable superhydride was predicted, which we attribute to the differences in the structures of the stable binary parents. △ Less

Submitted 19 April, 2026; originally announced April 2026.

A Software Package for Generating Robust and Accurate Potentials using the Moment Tensor Potential Framework

Authors: Josiah Roberts, Biswas Rijal, Simon Divilov, Jon-Paul Maria, William G. Fahrenholtz, Douglas E. Wolfe, Donald W. Brenner, Stefano Curtarolo, Eva Zurek

Abstract: We present the Plan for Robust and Accurate Potentials (PRAPs), a software package for training and using moment tensor potentials (MTPs) in concert with the Machine Learned Interatomic Potentials (MLIP) software package. PRAPs provides an automated workflow to train MTPs using active learning procedures, and a variety of utilities to ease and improve workflows when utilizing the MLIP software. PR… ▽ More We present the Plan for Robust and Accurate Potentials (PRAPs), a software package for training and using moment tensor potentials (MTPs) in concert with the Machine Learned Interatomic Potentials (MLIP) software package. PRAPs provides an automated workflow to train MTPs using active learning procedures, and a variety of utilities to ease and improve workflows when utilizing the MLIP software. PRAPs was originally developed in the context of crystal structure prediction, in which one calculates convex hulls and predicts low energy metastable and thermodynamically stable structures, but the potentials PRAPs develops are not limited to such applications. PRAPs produces two potentials, one capable of rough estimates of the energies, forces and stresses of almost any chemical structure in the specified compositional space -- the Robust Potential -- and a second potential intended to provide more accurate descriptions of ground state and metastable structures -- the Accurate Potential. We also present a Python library, mliputils, designed to assist users in working with the chemical structural files used by the MLIP package. △ Less

Submitted 13 December, 2025; originally announced December 2025.

Non-local Chemistry Driven by Cation-Anion Size Disparity in Helium Inserted Compounds under High Pressure

Authors: Zhen Liu, Stefano Raciopp, Katerina P. Hilleke, Abhiyan Pandit, Shuran Ma, Andreas Hermann, Dadong Yan, Eva Zurek, Mao-sheng Miao

Abstract: Opposing the theory that Helium (He) cannot be inserted into AB-type ionic compounds due to the Madelung energy increase, our crystal structure search and first-principles calculations found that He can form stable compounds with sodium halides (NaX, X=Cl, Br, I) under high-pressure. These reactions are driven by the non-local chemistry arising from the cation-anion size disparity, distinctly diff… ▽ More Opposing the theory that Helium (He) cannot be inserted into AB-type ionic compounds due to the Madelung energy increase, our crystal structure search and first-principles calculations found that He can form stable compounds with sodium halides (NaX, X=Cl, Br, I) under high-pressure. These reactions are driven by the non-local chemistry arising from the cation-anion size disparity, distinctly different from the He insertion reaction with A2B-type compounds. The large size differences between Na+ and X- enable structures that can effectively host He insertions through volume and inter-atomic distance disproportionation. Furthermore, the insertion of He atoms can significantly relieve the elevated Madelung energy that builds up in NaX under high pressure. This energy increase arises from structural transitions driven by cation-anion size disparity, which are necessary for reducing volume under pressure. The insertion of He allows the reduction of the total volume under high pressure without increasing the Madelung energy. Our predicted compounds and stability analysis reveal a new example of He reactivity governed not by local chemical bond formation, but by long-range electrostatic interactions. △ Less

Submitted 5 December, 2025; v1 submitted 28 November, 2025; originally announced November 2025.

Superionicity in Ammonium Polyhydrides at Extreme Pressures

Authors: Kyla de Villa, Xiaoyu Wang, Eva Zurek, Burkkhard Militzer

Abstract: Polyhydrides have been shown to form novel structures at high pressure, which may be found in the interiors of giant planets. With density functional molecular dynamics simulations we studied the behavior of ammonium polyhydride compounds with stoichiometries of NH$_7$, NH$_9$, NH$_{10}$, NH$_{11}$, NH$_{14}$, NH$_{20}$, and NH$_{24}$ which were predicted with crystal structure search methods to b… ▽ More Polyhydrides have been shown to form novel structures at high pressure, which may be found in the interiors of giant planets. With density functional molecular dynamics simulations we studied the behavior of ammonium polyhydride compounds with stoichiometries of NH$_7$, NH$_9$, NH$_{10}$, NH$_{11}$, NH$_{14}$, NH$_{20}$, and NH$_{24}$ which were predicted with crystal structure search methods to be metastable at 100-300~GPa. For every compound, we performed simulations at a range of temperatures (and for several compounds, pressures) covering the solid, superionic and liquid phases. We show that when heated, high pressure ammonium polyhydride compounds exhibit hydrogen superionic diffusion. We demonstrate a number of metrics by which the solid-to-superionic and superionic-to-liquid transitions can be detected from simulation data, including changes in the internal energy and pressure, formation of new chemical species, and atomic diffusion rates. We find that both the solid-to-superionic and the superionic-to-liquid transitions decrease in temperature as proton fraction increases. These trends indicate that above a proton fraction of $\sim$0.97, ammonium hydride structures are likely to directly melt instead of first exhibiting a superionic phase. Our observed melting trend further indicates that at the extreme conditions of ice giant interiors, hydrogen rich ammonium hydrides such as those studied in this work would exist predominantly as liquids rather than exhibiting a superionic phase. △ Less

Submitted 26 November, 2025; originally announced November 2025.

Novel Transformations of PbTiO3 with Pressure and Temperature

Authors: Husam Farraj, Stefano Racioppi, Gaston Garbarino, Muhtar Ahart, Anshuman Mondal, Samuel G. Parra, Jesse S. Smith, R. E. Cohen, Eva Zurek, Jordi Cabana, Russell J. Hemley

Abstract: We investigated the behavior of lead titanate (PbTiO3) up to 100 GPa, both at room temperature and upon laser heating, using synchrotron X ray diffraction combined with density functional theory (DFT) computations. At the high pressure temperature (PT) conditions produced in laser heated diamond anvil cells, PbTiO3 dissociates into PbO and TiO2, consistent with our DFT computations showing that de… ▽ More We investigated the behavior of lead titanate (PbTiO3) up to 100 GPa, both at room temperature and upon laser heating, using synchrotron X ray diffraction combined with density functional theory (DFT) computations. At the high pressure temperature (PT) conditions produced in laser heated diamond anvil cells, PbTiO3 dissociates into PbO and TiO2, consistent with our DFT computations showing that decomposition becomes enthalpically favored above 65 GPa. In contrast, on room temperature compression, PbTiO3 persists in the tetragonal I4mcm phase up to at least 100 GPa. Laser heating produces distinct PbO phases: a compressed form of alpha PbO and a previously unreported delta PbO polymorph, both of which transform to beta PbO on decompression. The calculations predict that alpha PbO undergoes pressure-induced band gap closure, metallizing above 70 GPa, whereas the delta and beta phases remain semiconducting with a band gap above 1 eV even at megabar pressures. The experimental and confirming theoretical results reveal an unanticipated dimension of the behavior of PbTiO3, showing that distinct equilibrium and metastable phases can be stabilized along different PT synthesis paths. △ Less

Submitted 29 January, 2026; v1 submitted 7 November, 2025; originally announced November 2025.

-Quantum Effects or Theoretical Artifacts? A Computational Reanalysis of Hydrogen's High-Pressure Phase Stability and Properties

Authors: Stefano Racioppi, Eva Zurek

Abstract: Experimental and theoretical studies of the high-pressure phases of hydrogen are highly sensitive to methodological choices. We compare the cold phase diagram of hydrogen calculated between 400-700 GPa with meta-GGA functionals (R2SCAN and SCAN0) with the commonly employed GGA-PBE functional. Molecular phases are stabilized over the atomic phase to higher pressures with the meta-GGA, in closer agr… ▽ More Experimental and theoretical studies of the high-pressure phases of hydrogen are highly sensitive to methodological choices. We compare the cold phase diagram of hydrogen calculated between 400-700 GPa with meta-GGA functionals (R2SCAN and SCAN0) with the commonly employed GGA-PBE functional. Molecular phases are stabilized over the atomic phase to higher pressures with the meta-GGA, in closer agreement with diffusion Monte Carlo calculations. R2SCAN phonon spectra show that the dynamical instabilities and anharmonic signatures predicted at the GGA level vanish, indicating that such effects may partly arise from functional deficiencies rather than quantum nuclear effects. Bonding analysis reveals that PBE artificially weakens intramolecular H-H bonds and enhances intermolecular interactions through charge delocalization, whereas meta-GGA preserves a more localized molecular character. △ Less

Submitted 15 June, 2026; v1 submitted 2 October, 2025; originally announced October 2025.

Single layer clathrane: A potential superconducting two-dimensional (2D) hydrogenated metal borocarbide

Authors: Xiaoyu Wang, Warren E. Pickett, Matthew N. Julian, Rohit P. Prasankumar, Eva Zurek

Abstract: We propose a new family of two-dimensional (2D) metal-borocarbide clathrane superconductors, derived from three-dimensional (3D) MM$^\prime$B$_6$C$_6$ clathrates. First-principles calculations reveal that hydrogen passivation and surface metal decoration stabilize the M$_2$M$^\prime$B$_8$C$_8$H$_8$ monolayers. These 2D systems exhibit tunable superconductivity governed by hole concentration, struc… ▽ More We propose a new family of two-dimensional (2D) metal-borocarbide clathrane superconductors, derived from three-dimensional (3D) MM$^\prime$B$_6$C$_6$ clathrates. First-principles calculations reveal that hydrogen passivation and surface metal decoration stabilize the M$_2$M$^\prime$B$_8$C$_8$H$_8$ monolayers. These 2D systems exhibit tunable superconductivity governed by hole concentration, structural anisotropy, and electron-phonon coupling. We find that in-plane anisotropy competes with superconductivity, reducing \tc\ despite favorable doping. Biaxial strain mitigates this anisotropy, enhances Fermi surface nesting, and increases \tc\ by an average of 15.5~K. For example, the \tc\ of Sr$_3$B$_8$C$_8$H$_8$ is predicted to increase from 11.3~K to 22.2~K with strain engineering. These findings identify 2D clathranes as promising, strain-tunable superconductors and highlight design principles for optimizing low-dimensional superconducting materials. △ Less

Submitted 19 August, 2025; originally announced August 2025.

Using Topology to Predict Electrides in the Solid State

Authors: Stefano Racioppi, Eva Zurek

Abstract: Electrides are characterized by electron density highly localized in interstitial sites, which do not coincide with the interatomic contacts. The rigorous quantum mechanical definition of electrides is based upon topological criteria derived from the electron density, and in particular the presence of non-nuclear attractors (NNAs). We employ these topological criteria in combination with crystal s… ▽ More Electrides are characterized by electron density highly localized in interstitial sites, which do not coincide with the interatomic contacts. The rigorous quantum mechanical definition of electrides is based upon topological criteria derived from the electron density, and in particular the presence of non-nuclear attractors (NNAs). We employ these topological criteria in combination with crystal structure prediction methods (the XtalOpt evolutionary algorithm), to accelerate the discovery of crystalline electrides at ambient and non-ambient pressures. The localization and quantification of NNAs is used as the primary discriminator for the electride character of a solid within a multi-objective evolutionary structure search. We demonstrate the reliability of this approach through a comprehensive crystal structure prediction study of Ca5Pb3 at 20 GPa, a system previously theorized to exhibit electride character under compression. Our strategy could predict, and sort on-the-fly, several unknown low-enthalpy phases that possess NNAs in interstitial loci, such as the newly discovered P4/mmm structure. These results demonstrate how evolutionary algorithms, guided by rigorous topological descriptors, can be relied upon to effectively survey complex phases to find new electride candidates. △ Less

Submitted 6 August, 2025; originally announced August 2025.

Refining Tc Prediction in Hydrides via Symbolic-Regression-Enhanced Electron-Localization-Function-Based Descriptors

Authors: Francesco Belli, Sean Torres, Julia Contreras-Garcìa, Eva Zurek

Abstract: Hydrogen-based materials are able to possess extremely high superconducting critical temperatures, \tc s, due to hydrogen's low atomic mass and strong electron-phonon interaction. Recently, a descriptor based on the Electron Localization Function (ELF) has enabled the rapid estimation of the \tc\ of hydrogen-containing compounds from electronic networking properties, but its applicability has been… ▽ More Hydrogen-based materials are able to possess extremely high superconducting critical temperatures, \tc s, due to hydrogen's low atomic mass and strong electron-phonon interaction. Recently, a descriptor based on the Electron Localization Function (ELF) has enabled the rapid estimation of the \tc\ of hydrogen-containing compounds from electronic networking properties, but its applicability has been limited by the small size and homogeneity of the training dataset used. Herein, the model is re-examined compiling a publicly available combined dataset of 244 binary and ternary hydride superconductors. Our analysis shows that though ELF-based networking remains a valuable descriptor, its predictive power declines with increasing compositional complexity. However, by introducing the molecularity index, defined as the highest value of the ELF at which two hydrogen atoms connect, and applying symbolic regression, the accuracy of the predictions can be substantially enhanced. These results establish a more robust framework for assessing superconductivity in hydride materials, facilitating accelerated screening of novel candidates through integration with crystal structure prediction methods or high-throughput searches. △ Less

Submitted 20 June, 2025; originally announced June 2025.

Comments: 13 pates,4 figures

ACM Class: J.2

XtalOpt Version 14: Variable-Composition Crystal Structure Search for Functional Materials Through Pareto Optimization

Authors: Samad Hajinazar, Eva Zurek

Abstract: Version 14 of XtalOpt, an evolutionary multi-objective global optimization algorithm for crystal structure prediction, is now available for download from its official website https://xtalopt.github.io, and the Computer Physics Communications Library. The new version of the code is designed to perform a ground state search for crystal structures with variable compositions by integrating a suite of… ▽ More Version 14 of XtalOpt, an evolutionary multi-objective global optimization algorithm for crystal structure prediction, is now available for download from its official website https://xtalopt.github.io, and the Computer Physics Communications Library. The new version of the code is designed to perform a ground state search for crystal structures with variable compositions by integrating a suite of ab initio methods alongside classical and machine-learning potentials for structural relaxation. The multi-objective search framework has been enhanced through the introduction of Pareto optimization, enabling efficient discovery of functional materials. Herein, we describe the newly implemented methodologies, provide detailed instructions for their use, and present an overview of additional improvements included in the latest version of the code. △ Less

Submitted 10 December, 2025; v1 submitted 7 June, 2025; originally announced June 2025.

Theoretical Predictions of MB5N5: Atom-Stuffed Boronitride Clathrate Cages Derived from the High-Pressure Superhydride

Authors: Nisha Geng, Giacomo Scilla, Eva Zurek

Abstract: This study investigates 198 MX5Y5 (X, Y = B, C, or N) clathrate-like structures derived from MH10 superhydrides using high-throughput Density Functional Theory (DFT) geometry optimizations and phonon calculations. A wide variety of electropositive and electronegative encapsulated atoms were considered. From all of the studied systems only 34 MB5N5 phases were found to be dynamically stable at ambi… ▽ More This study investigates 198 MX5Y5 (X, Y = B, C, or N) clathrate-like structures derived from MH10 superhydrides using high-throughput Density Functional Theory (DFT) geometry optimizations and phonon calculations. A wide variety of electropositive and electronegative encapsulated atoms were considered. From all of the studied systems only 34 MB5N5 phases were found to be dynamically stable at ambient pressure. The highest 1-atmosphere superconducting critical transition temperature was predicted for FB5N5. However, ab initio molecular dynamics simulations revealed that all of the identified superconducting phases decompose by 300~K at 1~atm, while only eleven semiconducting phases remained thermally stable. Our findings underscore the critical role of kinetic and thermal stability in predicting viable superconductors. The electronic structure of the MB5N5 compounds were rationalized in terms of electron donating and withdrawing intercalants, and machine-learning based predictions of their mechanical properties were compared with those of an empty boronitride cage. △ Less

Submitted 17 April, 2025; v1 submitted 10 February, 2025; originally announced February 2025.

Creation, stabilization, and study at ambient pressure of pressure-induced superconductivity in Bi$_{0.5}$Sb$_{1.5}$Te$_3$

Authors: Liangzi Deng, Busheng Wang, Clayton Halbert, Daniel J. Schulze, Melissa Gooch, Trevor Bontke, Ting-Wei Kuo, Xin Shi, Shaowei Song, Nilesh Salke, Hung-Duen Yang, Zhifeng Ren, Russell J. Hemley, Eva Zurek, Rohit P. Prasankumar, Ching-Wu Chu

Abstract: In light of breakthroughs in superconductivity under high pressure, and considering that record critical temperatures (T$_c$s) across various systems have been achieved under high pressure, the primary challenge for higher Tc should no longer solely be to increase T$_c$ under extreme conditions but also to reduce, or ideally eliminate, the need for applied pressure in retaining pressure-induced or… ▽ More In light of breakthroughs in superconductivity under high pressure, and considering that record critical temperatures (T$_c$s) across various systems have been achieved under high pressure, the primary challenge for higher Tc should no longer solely be to increase T$_c$ under extreme conditions but also to reduce, or ideally eliminate, the need for applied pressure in retaining pressure-induced or -enhanced superconductivity. The topological semiconductor Bi$_{0.5}$Sb$_{1.5}$Te$_3$ (BST) was chosen to demonstrate our approach to addressing this challenge and exploring its intriguing physics. Under pressures up to ~ 50 GPa, three superconducting phases (BST-I, -II, and -III) were observed. A superconducting phase in BST-I appears at ~ 4 GPa, without a structural transition, suggesting the possible topological nature of this phase. Using the pressure-quench protocol (PQP) recently developed by us, we successfully retained this pressure-induced phase at ambient pressure and revealed the bulk nature of the state. Significantly, this demonstrates recovery of a pressure-quenched sample from a diamond anvil cell at room temperature with the pressure-induced phase retained at ambient pressure. Other superconducting phases were retained in BST-II and -III at ambient pressure and subjected to thermal and temporal stability testing. Superconductivity was also found in BST with T$_c$ up to 10.2 K, the record for this compound series. While PQP maintains superconducting phases in BST at ambient pressure, both depressurization and PQP enhance its T$_c$, possibly due to microstructures formed during these processes, offering an added avenue to raise T$_c$. These findings are supported by our density-functional theory calculations. △ Less

Submitted 3 February, 2025; originally announced February 2025.

Comments: 26 pages, 14 figures

A chemical bonding based descriptor for predicting the impact of quantum nuclear and anharmonic effects on hydrogen-based superconductors

Authors: Francesco Belli, Eva Zurek, Ion Errea

Abstract: Quantum nuclear effects (QNEs) can significantly alter a material's crystal structure and phonon spectra, impacting properties such as thermal conductivity and superconductivity. However, predicting a priori whether these effects will enhance or suppress superconductivity, or destabilize a structure, remains a grand challenge. Herein, we address this unresolved problem by introducing a descriptor,… ▽ More Quantum nuclear effects (QNEs) can significantly alter a material's crystal structure and phonon spectra, impacting properties such as thermal conductivity and superconductivity. However, predicting a priori whether these effects will enhance or suppress superconductivity, or destabilize a structure, remains a grand challenge. Herein, we address this unresolved problem by introducing a descriptor, based upon the integrated crystal orbital bonding index (iCOBI), to predict the influence of QNEs on a crystal lattice's dynamic stability, phonon spectra and superconducting properties. We find that structures with atoms in symmetric chemical bonding environments exhibit greater resilience to structural perturbations induced by QNEs, while those with atoms in asymmetric bonding environments are more susceptible to structural alterations, resulting in enhanced superconducting critical temperatures. △ Less

Submitted 24 January, 2025; originally announced January 2025.

Quantum Anharmonic Effects on the Superconductivity of I-43m CH4-H3S at High Pressures: a First-Principles Study

Authors: Pugeng Hou, Francesco Belli, Tiange Bi, Eva Zurek, Ion Errea

Abstract: Making use of first-principles calculations we analyze the effect of quantum ionic fluctuations and lattice anharmonicity on the crystal structure and superconductivity of I-43m CH4-H3S, one of the lowest enthalpy structures in the C-S-H system, in the 150-300 GPa pressure range within the stochastic self-consistent harmonic approximation. We predict a correction to the crystal structure, which is… ▽ More Making use of first-principles calculations we analyze the effect of quantum ionic fluctuations and lattice anharmonicity on the crystal structure and superconductivity of I-43m CH4-H3S, one of the lowest enthalpy structures in the C-S-H system, in the 150-300 GPa pressure range within the stochastic self-consistent harmonic approximation. We predict a correction to the crystal structure, which is formed by an H3S lattice and CH4 molecules, the phonon spectra, and the pressure-dependent superconducting critical temperatures, which have been estimated in previous calculations without considering ionic fluctuations on the crystal structure and assuming the harmonic approximation for the lattice dynamics. Our results show that quantum ionic fluctuations have an impact on the distance between H atoms and S atoms in the H3S host lattice, pushing it towards more symmetric bonds, while the methane molecules are barely affected. According to our anharmonic phonon spectra, this structure is dynamically stable above 150 GPa, which is 30 GPa lower than the pressure at which the harmonic approximation predicts the emergence of an instability. As a consequence of the strong anharmonic enhancement of the phonon frequencies, the electron-phonon coupling constant is suppressed by 46% at 200 GPa, and even more at lower pressures. As a result, the superconducting critical temperature is overestimated by around 50 K at 200 GPa, such that it falls below 150 K in the whole pressure range studied. Our results underline that ternary hydrides are subject to strong anharmonic effects on their structural, vibrational, and superconducting properties. △ Less

Submitted 24 December, 2024; originally announced December 2024.

Comments: arXiv admin note: substantial text overlap with arXiv:2107.08669; text overlap with arXiv:2102.00072

ACM Class: J.2.9

Why Mg$_2$IrH$_6$ is predicted to be a high temperature superconductor, but Ca$_2$IrH$_6$ is not

Authors: Xiaoyu Wang, Warren Pickett, Micheal Hutcheon, Rohit Prasankumar, Eva Zurek

Abstract: The X$_2$MH$_6$ family, consisting of an electropositive cation X and a main group metal M octahedrally coordinated by hydrogen, has been predicted to hold promise for high-temperature conventional superconductivity. Herein, we analyze the electronic structure of two members of this family, Mg$_2$IrH$_6$ and Ca$_2$IrH$_6$, showing why the former may possess superconducting properties rivaling thos… ▽ More The X$_2$MH$_6$ family, consisting of an electropositive cation X and a main group metal M octahedrally coordinated by hydrogen, has been predicted to hold promise for high-temperature conventional superconductivity. Herein, we analyze the electronic structure of two members of this family, Mg$_2$IrH$_6$ and Ca$_2$IrH$_6$, showing why the former may possess superconducting properties rivaling those of the cuprates, whereas the latter does not. Within Mg$_2$IrH$_6$ the vibrations of the IrH$_6^{4-}$ anions are key for the superconducting mechanism, and they induce coupling in the $e_g^*$ set, which are antibonding between the H 1$s$ and the Ir $d_{x^2-y^2}$ or $d_{z^2}$ orbitals. Because calcium possesses low-lying d-orbitals, $e_g^* \rightarrow$ Ca $d$ back-donation is preferred, quenching the superconductivity. Our analysis explains why high critical temperatures were only predicted for second or third row X metal atoms, and may hold implications for superconductivity in other systems where the antibonding anionic states are filled. △ Less

Submitted 15 July, 2024; originally announced July 2024.

Powder X-Ray Diffraction Assisted Evolutionary Algorithm for Crystal Structure Prediction

Authors: Stefano Racioppi, Alberto Otero De la Roza, Samad Hajinazar, Eva Zurek

Abstract: Experimentally obtained X-ray diffraction (XRD) patterns can be difficult to solve, precluding the full characterization of materials, pharmaceuticals, and geological compounds. Herein, we propose a method based upon a multi-objective evolutionary search that uses both a structure's enthalpy and similarity to a reference XRD pattern (constituted by a list of peak positions and their intensities) t… ▽ More Experimentally obtained X-ray diffraction (XRD) patterns can be difficult to solve, precluding the full characterization of materials, pharmaceuticals, and geological compounds. Herein, we propose a method based upon a multi-objective evolutionary search that uses both a structure's enthalpy and similarity to a reference XRD pattern (constituted by a list of peak positions and their intensities) to facilitate structure solution of inorganic systems. Because the similarity index is computed for locally optimized cells that are subsequently distorted to find the best match with the reference, this process transcends both computational (e.g. choice of theoretical method, and 0 K approximation) and experimental (e.g. external stimuli, and metastability) limitations. We illustrate how the proposed methodology can be employed to successfully uncover complex crystal structures by applying it to a range of test cases, including inorganic minerals, pure elements ramp-compressed to extreme conditions, and molecular crystals. The results demonstrate that our approach not only improves the accuracy of structure prediction but also significantly reduces the time required to achieve reliable solutions, thus providing a powerful tool for the advancement of materials science and related fields. △ Less

Submitted 7 July, 2024; originally announced July 2024.

Impact of Data Bias on Machine Learning for Crystal Compound Synthesizability Predictions

Authors: Ali Davariashtiyani, Busheng Wang, Samad Hajinazar, Eva Zurek, Sara Kadkhodaei

Abstract: Machine learning models are susceptible to being misled by biases in training data that emphasize incidental correlations over the intended learning task. In this study, we demonstrate the impact of data bias on the performance of a machine learning model designed to predict the synthesizability likelihood of crystal compounds. The model performs a binary classification on labeled crystal samples.… ▽ More Machine learning models are susceptible to being misled by biases in training data that emphasize incidental correlations over the intended learning task. In this study, we demonstrate the impact of data bias on the performance of a machine learning model designed to predict the synthesizability likelihood of crystal compounds. The model performs a binary classification on labeled crystal samples. Despite using the same architecture for the machine learning model, we showcase how the model's learning and prediction behavior differs once trained on distinct data. We use two data sets for illustration: a mixed-source data set that integrates experimental and computational crystal samples and a single-source data set consisting of data exclusively from one computational database. We present simple procedures to detect data bias and to evaluate its effect on the model's performance and generalization. This study reveals how inconsistent, unbalanced data can propagate bias, undermining real-world applicability even for advanced machine learning techniques. △ Less

Submitted 25 June, 2024; originally announced June 2024.

Comments: 8 pages, 4 figures, 3 appendices

Efficient Modelling of Anharmonicity and Quantum Effects in PdCuH$_2$ with Machine Learning Potentials

Authors: Francesco Belli, Eva Zurek

Abstract: Quantum nuclear effects and anharmonicity impact a wide range of functional materials and their properties. One of the most powerful techniques to model these effects is the Stochastic Self-Consistent Harmonic Approximation (SSCHA). Unfortunately, the SSCHA is extremely computationally expensive, prohibiting its routine use. We propose a protocol that pairs machine learning interatomic potentials,… ▽ More Quantum nuclear effects and anharmonicity impact a wide range of functional materials and their properties. One of the most powerful techniques to model these effects is the Stochastic Self-Consistent Harmonic Approximation (SSCHA). Unfortunately, the SSCHA is extremely computationally expensive, prohibiting its routine use. We propose a protocol that pairs machine learning interatomic potentials, which can be tailored for the system at hand via active learning, with the SSCHA. Our method leverages an upscaling procedure that allows for the treatment of supercells of up to thousands of atoms with practically minimal computational effort. The protocol is applied to PdCuH$_x$ ($x = 0-2$) compounds, chosen because previous experimental studies have reported superconducting critical temperatures, $T_\text{c}$s, as high as 17~K at ambient pressures in an unknown hydrogenated PdCu phase. We identify a $P4/mmm$ PdCuH$_2$ structure, which is shown to be dynamically stable only upon the inclusion of quantum fluctuations, as being a key contributor to the measured superconductivity. For this system, our methodology is able to reduce the computational expense for the SSCHA calculations by $\sim$96\%. The proposed protocol opens the door towards the routine inclusion of quantum nuclear motion and anharmonicity in materials discovery. △ Less

Submitted 17 January, 2025; v1 submitted 18 June, 2024; originally announced June 2024.

MSC Class: 82Dxx ACM Class: J.2

Predicted High-Pressure Hot Superconductivity in Li$_2$CaH$_{16}$ and Li$_2$CaH$_{17}$ Phases that Resemble the Type-II Clathrate Structure

Authors: Morgan Redington, Eva Zurek

Abstract: High-temperature high-pressure superconducting hydrides are typically characterized by cage-like hydrogenic lattices filled with electropositive metal atoms. Here, density functional theory based evolutionary crystal structure searches find two phases that possess these geometric features and are related to the Type-II clathrate structure. In these $Fd\overline{3}m$ Li$_2$CaH$_{16}$ and… ▽ More High-temperature high-pressure superconducting hydrides are typically characterized by cage-like hydrogenic lattices filled with electropositive metal atoms. Here, density functional theory based evolutionary crystal structure searches find two phases that possess these geometric features and are related to the Type-II clathrate structure. In these $Fd\overline{3}m$ Li$_2$CaH$_{16}$ and $R\overline{3}m$ Li$_2$CaH$_{17}$ phases the calcium atom occupies the larger cage and the lithium atom the smaller one. The highest superconducting critical temperatures predicted within the isotropic Eliashberg formalism, 330~K at 350~GPa for $Fd\overline{3}m$ Li$_2$CaH$_{16}$ and 370~K at 300~GPa for $R\overline{3}m$ Li$_2$CaH$_{17}$, suggest these structures fall in the class of high-energy-density quantum materials known as hot superconductors. As pressure is lowered the cage-like lattices distort with the emergence of quasimolecular hydrogenic motifs; nonetheless Li$_2$CaH$_{17}$ is predicted to be superconducting down to 160~GPa at 205~K. △ Less

Submitted 17 September, 2024; v1 submitted 28 May, 2024; originally announced May 2024.

Comments: 35 pages, 5 figures

Journal ref: Chemistry of Materials 2024, 36 (17), 8412-8423

Superconductivity in Dilute Hydrides of Ammonia under Pressure

Authors: Xiaoyu Wang, Nisha Geng, Kyla de Villa, Burkard Militzer, Eva Zurek

Abstract: In the last decade, there has been great progress in predicting and synthesizing polyhydrides that exhibit superconductivity when squeezed. Dopants allow these compounds to become metals at pressures lower than those required to metallize elemental hydrogen. Here, we show that by combining the fundamental planetary building blocks of molecular hydrogen and ammonia, conventional superconducting com… ▽ More In the last decade, there has been great progress in predicting and synthesizing polyhydrides that exhibit superconductivity when squeezed. Dopants allow these compounds to become metals at pressures lower than those required to metallize elemental hydrogen. Here, we show that by combining the fundamental planetary building blocks of molecular hydrogen and ammonia, conventional superconducting compounds can be formed at high pressure. Through extensive theoretical calculations we predict metallic metastable structures with NH$_n$ ($n=10,11,24$) stoichiometries that are based on NH$_4^+$ superalkali cations and complex hydrogenic lattices. The hydrogen atoms in the molecular cation contribute to the superconducting mechanism, and the estimated superconducting critical temperatures, $T_\text{c}$s, are comparable to the highest values computed for the alkali metal polyhydrides. The largest calculated (isotropic Eliashberg) $T_\text{c}$ is 179~K for $Pnma$-NH$_{10}$ at 300~GPa. Our results suggest that other molecular cations can be mixed with hydrogen under pressure yielding superconducting compounds. △ Less

Submitted 18 May, 2024; originally announced May 2024.

XtalOpt Version 13: Multi-Objective Evolutionary Search for Novel Functional Materials

Authors: Samad Hajinazar, Eva Zurek

Abstract: Version 13 of XtalOpt, an evolutionary algorithm for crystal structure prediction, is now available for download from the CPC program library or the XtalOpt website, https://xtalopt.github.io. In the new version of the XtalOpt code, a general platform for multi-objective global optimization is implemented. This functionality is designed to facilitate the search for (meta)stable phases of functiona… ▽ More Version 13 of XtalOpt, an evolutionary algorithm for crystal structure prediction, is now available for download from the CPC program library or the XtalOpt website, https://xtalopt.github.io. In the new version of the XtalOpt code, a general platform for multi-objective global optimization is implemented. This functionality is designed to facilitate the search for (meta)stable phases of functional materials through minimization of the enthalpy of a crystalline system coupled with the simultaneous optimization of any desired properties that are specified by the user. The code is also able to perform a constrained search by filtering the parent pool of structures based on a user-specified feature, while optimizing multiple objectives. Here, we present the implementation and various technical details, and we provide a brief overview of additional improvements that have been introduced in the new version of XtalOpt. △ Less

Submitted 19 June, 2024; v1 submitted 3 May, 2024; originally announced May 2024.

Quantum Stabilization and Flat Hydrogen-based Bands of Nitrogen-doped Lutetium Hydride

Authors: Adam Denchfield, Francesco Belli, Eva Zurek, Hyowon Park, Russell J Hemley

Abstract: We explore electronic and structural properties of Fm$\overline{3}$m Lu-H-N structures with specific N,H ordering as plausible candidates for near-ambient superconductivity possibly originating from their remarkably narrow hydrogen-based bands at the Fermi level. Although LuH$_{2.875}$N$_{0.125}$ exhibits an instability persisting up to 17 GPa, it is anharmonically stable near ambient pressure whe… ▽ More We explore electronic and structural properties of Fm$\overline{3}$m Lu-H-N structures with specific N,H ordering as plausible candidates for near-ambient superconductivity possibly originating from their remarkably narrow hydrogen-based bands at the Fermi level. Although LuH$_{2.875}$N$_{0.125}$ exhibits an instability persisting up to 17 GPa, it is anharmonically stable near ambient pressure when accounting for quantum nuclear effects. The presence of flat bands near $E_\text{F}$ is understood to arise from destructive\ quantum interference between N-p and surrounding H-s orbitals, with certain types of defects leaving the flat bands unaffected. The results suggest there is an optimal pressure near ambient where the superconducting $T_{\text{c}}$ is maximized in this structure by anharmonically-stabilized low-frequency and non-adiabatically coupled high-frequency hydrogen modes. Despite the metastability of this structure, its electronic properties and dynamical stability when calculated beyond a classical harmonic approach can explain the reported near-ambient superconductivity in Lu-H-N. △ Less

Submitted 23 June, 2024; v1 submitted 2 March, 2024; originally announced March 2024.

Comments: Added significant supplemental information since previous version, revised main figures and text. Conclusions unchanged from previous version but additional insight uncovered regarding pressure dependence. 7 main figures and 11 SI figures

Machine Learned Interatomic Potentials for Ternary Carbides trained on the AFLOW Database

Authors: Josiah Roberts, Biswas Rijal, Simon Divilov, Jon-Paul Maria, William G. Fahrenholtz, Douglas E. Wolfe, Donald W. Brenner, Stefano Curtarolo, Eva Zurek

Abstract: Large density functional theory (DFT) databases are a treasure trove of energies, forces and stresses that can be used to train machine learned interatomic potentials for atomistic modeling. Herein, we employ structural relaxations from the AFLOW database to train moment tensor potentials (MTPs) for four carbide systems: HfTaC, HfZrC, MoWC and TaTiC. The resulting MTPs are used to relax ~6300 rand… ▽ More Large density functional theory (DFT) databases are a treasure trove of energies, forces and stresses that can be used to train machine learned interatomic potentials for atomistic modeling. Herein, we employ structural relaxations from the AFLOW database to train moment tensor potentials (MTPs) for four carbide systems: HfTaC, HfZrC, MoWC and TaTiC. The resulting MTPs are used to relax ~6300 random symmetric structures, and are subsequently improved via active learning to generate robust potentials (RP) that can relax a wide variety of structures, and accurate potentials (AP) designed for the relaxation of low-energy systems. This protocol is shown to yield convex hulls that are indistinguishable from those predicted by AFLOW for the HfTaC, HfZrC and TaTiC systems, and in the case of the MoWC system to predict thermodynamically stable structures that are not found within AFLOW, highlighting the potential of the employed protocol within crystal structure prediction. Relaxation of over three hundred Mo$_{1-x}$W$_x$C stoichiometry crystals first with the RP then with the AP yields formation enthalpies that are in excellent agreement with those obtained via DFT. △ Less

Submitted 16 May, 2024; v1 submitted 3 January, 2024; originally announced January 2024.

Superconductivity in CH4 and BH4- Containing Compounds Derived from the High-Pressure Superhydrides

Authors: Nisha Geng, Katerina P. Hilleke, Francesco Belli, Pratik Kumar Das, Eva Zurek

Abstract: Inspired by the synthesis of the high-pressure Fm-3m LaH10 superconducting superhydride, systematic density functional theory (DFT) calculations are performed to study ternaries that could be derived from it by replacing two of the hydrogen atoms with boron or carbon and varying the identity of the electropositive element. Though many of the resulting alkali-metal and alkaline-earth MC2H8 phases a… ▽ More Inspired by the synthesis of the high-pressure Fm-3m LaH10 superconducting superhydride, systematic density functional theory (DFT) calculations are performed to study ternaries that could be derived from it by replacing two of the hydrogen atoms with boron or carbon and varying the identity of the electropositive element. Though many of the resulting alkali-metal and alkaline-earth MC2H8 phases are predicted to be dynamically stable at mild pressures, their superconducting critical temperatures (Tcs) are low because their metallicity results from the filling of an electride-like band. Substitution with a trivalent element leads to phases with substantial metal d-character at the Fermi level whose Tcs are typically above 40 K. Among the MB2H8 phases examined, KB2H8, RbB2H8 and CsB2H8 are predicted to be dynamically stable at very mild pressures, and their stability is rationalized by a DFT-Chemical Pressure analysis that elucidates the role of the M atom size. Quantum anharmonic effects strongly affect the properties of KB2H8, the highest predicted Tc compound, near 10 GPa, but molecular dynamics simulations reveal it would decompose below its Tc at this pressure. Nonetheless, at ca. 50 GPa KB2H8 is predicted to be thermally stable with a superconducting figure of merit surpassing that of the recently synthesized LaBeH8. △ Less

Submitted 29 December, 2023; originally announced January 2024.

Phase Boundaries, Isotope Effect and Superconductivity of Lithium Under Hydrostatic Conditions

Authors: Stefano Racioppi, Iren Saffarian-Deemyad, William Holle, Francesco Belli, Richard Ferry, Curtis Kenney-Benson, Jesse S. Smith, Eva Zurek, Shanti Deemyad

Abstract: We present theoretical and experimental studies of superconductivity and low temperature structural phase boundaries in lithium. We mapped the structural phase diagram of 6Li and 7Li under hydrostatic conditions between 5 top 55GPa and within the temperature range of 15 to 75K, observing the FCC-hR1-cI16 phase transitions. 6Li and 7Li show some differences at the structural boundaries, with a pote… ▽ More We present theoretical and experimental studies of superconductivity and low temperature structural phase boundaries in lithium. We mapped the structural phase diagram of 6Li and 7Li under hydrostatic conditions between 5 top 55GPa and within the temperature range of 15 to 75K, observing the FCC-hR1-cI16 phase transitions. 6Li and 7Li show some differences at the structural boundaries, with a potential shift of the phase boundaries of 6Li to lower pressures. Density functional theory calculations and topological analysis of the electron density elucidates the superconducting properties and interatomic interactions within these phases of lithium. △ Less

Submitted 4 January, 2024; v1 submitted 29 December, 2023; originally announced December 2023.

Comments: (24 pages, 10 figures, 2 tables, 2 parts including main manuscript and the supplementary information section)

A priori procedure to establish spinodal decomposition in alloys

Authors: Simon Divilov, Hagen Eckert, Cormac Toher, Rico Friedrich, Adam C. Zettel, Donald W. Brenner, William G. Fahrenholtz, Douglas E. Wolfe, Eva Zurek, Jon-Paul Maria, Nico Hotz, Xiomara Campilongo, Stefano Curtarolo

Abstract: Spinodal decomposition can improve a number of essential properties in materials, especially hardness. Yet, the theoretical prediction of the onset of this phenomenon (e.g., temperature) and its microstructure (e.g., wavelength) often requires input parameters coming from costly and time-consuming experimental efforts, hindering rational materials optimization. Here, we present a procedure where s… ▽ More Spinodal decomposition can improve a number of essential properties in materials, especially hardness. Yet, the theoretical prediction of the onset of this phenomenon (e.g., temperature) and its microstructure (e.g., wavelength) often requires input parameters coming from costly and time-consuming experimental efforts, hindering rational materials optimization. Here, we present a procedure where such parameters are not derived from experiments. First, we calculate the spinodal temperature by modeling nucleation in the solid solution while approaching the spinode boundary. Then, we compute the spinodal wavelength self-consistently using a few reasonable approximations. Our results show remarkable agreement with experiments and, for NiRh, the calculated yield strength due to spinodal microstructures surpasses even those of Ni-based superalloys. We believe that this procedure will accelerate the exploration of the complex materials experiencing spinodal decomposition, critical for their macroscopic properties. △ Less

Submitted 17 November, 2023; originally announced November 2023.

Comments: 10 pages, 4 figures

On the Electride Nature of Na-hP4

Authors: Stefano Racioppi, Christian V. Storm, Malcolm I. McMahon, Eva Zurek

Abstract: Early quantum mechanical models suggested that pressure drives solids towards free-electron metal behavior where the ions are locked into simple close-packed structures. The prediction and subsequent discovery of high-pressure electrides (HPEs), compounds assuming open structures where the valence electrons are localized in interstitial voids, required a paradigm shift. Our quantum chemical calcul… ▽ More Early quantum mechanical models suggested that pressure drives solids towards free-electron metal behavior where the ions are locked into simple close-packed structures. The prediction and subsequent discovery of high-pressure electrides (HPEs), compounds assuming open structures where the valence electrons are localized in interstitial voids, required a paradigm shift. Our quantum chemical calculations on the iconic insulating Na-hP4 HPE show that increasing density causes a 3s -> 3pd electronic transition due to Coulomb repulsion between the 1s2s and 3s states, and orthogonality of the 3pd states to the core. The large lobes of the resulting Na-pd hybrid orbitals point towards the center of an 11-membered penta-capped trigonal prism and overlap constructively, forming multi-centered bonds, which are responsible for the emergence of the interstitial charge localization in Na-hP4. These multi-centered bonds facilitate the increased density of this phase, which is key for its stabilization under pressure. △ Less

Submitted 2 November, 2023; originally announced November 2023.

Journal ref: Angew. Chem. Int. Ed. 2023, e202310802

Interfacial defect properties of high-entropy carbides: Stacking faults, Shockley partial dislocations, and a new Evans-Polanyi-Semenov relation

Authors: Samuel E. Daigle, Stefano Curtarolo, William G. Fahrenholtz, Jon-Paul Maria, Douglas E. Wolfe, Eva Zurek, Donald W. Brenner

Abstract: Using first principles calculations, {111} intrinsic stacking fault (ISF) energies in Group IVB, VB, and VIB high-entropy transition metal carbides are shown to be predictable from an optimized rule of mixtures based on the properties of the single metal carbide constituents present near the stacking fault. A composition-independent linear relationship is demonstrated between the ISF energies and… ▽ More Using first principles calculations, {111} intrinsic stacking fault (ISF) energies in Group IVB, VB, and VIB high-entropy transition metal carbides are shown to be predictable from an optimized rule of mixtures based on the properties of the single metal carbide constituents present near the stacking fault. A composition-independent linear relationship is demonstrated between the ISF energies and the unstable stacking fault (USF) energies along the <112>{111} gamma surface slip path. Treating the ISF and USF energies as analogous to the heat of reaction and transition state barrier in chemical reactions, this linear relationship represents a new application of the Evans-Polanyi-Semenov principle. Further, a full defect energy distribution can be obtained from the predicted ISF energies with only the composition as an input for the mixed early-transition metal carbides. Applying a model that balances the elastic repulsion between partial dislocations with the distribution of ISF energies, we show that Shockley partial edge dislocations should remain bound for all valence electron concentration values up to about 9.6, even when the average stacking fault energy is negative. △ Less

Submitted 23 November, 2024; v1 submitted 1 November, 2023; originally announced November 2023.

Comments: 10 pages

Structurally Constrained Evolutionary Algorithm for the Discovery and Design of Metastable Phases

Authors: Busheng Wang, Katerina P. Hilleke, Samad Hajinazar, Gilles Frapper, Eva Zurek

Abstract: Metastable materials are abundant in nature and technology, showcasing remarkable properties that inspire innovative materials design. However, traditional crystal structure prediction methods, which rely solely on energetic factors to determine a structure's fitness, are not suitable for predicting the vast number of potentially synthesizable phases that represent a local minimum corresponding to… ▽ More Metastable materials are abundant in nature and technology, showcasing remarkable properties that inspire innovative materials design. However, traditional crystal structure prediction methods, which rely solely on energetic factors to determine a structure's fitness, are not suitable for predicting the vast number of potentially synthesizable phases that represent a local minimum corresponding to a state in thermodynamic equilibrium. Here, we present a new approach for the prediction of metastable phases with specific structural features, and interface this method with the XtalOpt evolutionary algorithm. Our method relies on structural features that include the local crystalline order (e.g., the coordination number or chemical environment), and symmetry (e.g., Bravais lattice and space group) to filter the parent pool of an evolutionary crystal structure search. The effectiveness of this approach is benchmarked on three known metastable systems: XeN$_8$, with a two-dimensional polymeric nitrogen sublattice, brookite TiO$_2$, and a high pressure BaH$_4$ phase that was recently characterized. Additionally, a newly predicted metastable melaminate salt, $P$-1 WC$_{3}$N$_{6}$, was found to possess an energy that is lower than two phases proposed in a recent computational study. The method presented here could help in identifying the structures of compounds that have already been synthesized, and developing new synthesis targets with desired properties. △ Less

Submitted 1 November, 2023; v1 submitted 2 June, 2023; originally announced June 2023.

Journal ref: J. Chem. Theory Comput. 2023, 19, 21, 7960

Structure, Stability and Superconductivity of N-doped Lutetium Hydrides at kbar Pressures

Authors: Katerina P. Hilleke, Xiaoyu Wang, Dongbao Luo, Nisha Geng, Busheng Wang, Eva Zurek

Abstract: The structure of the material responsible for the room temperature and near ambient pressure superconductivity reported in an N-doped lutetium hydride [Nature, 615, 244 (2023)] has not been conclusively determined. Herein, density functional theory calculations are performed in an attempt to uncover what it might be. Guided by a range of strategies including crystal structure prediction and modifi… ▽ More The structure of the material responsible for the room temperature and near ambient pressure superconductivity reported in an N-doped lutetium hydride [Nature, 615, 244 (2023)] has not been conclusively determined. Herein, density functional theory calculations are performed in an attempt to uncover what it might be. Guided by a range of strategies including crystal structure prediction and modifications of existing structure types, we present an array of Lu-N-H phases that are dynamically stable at experimentally relevant pressures. Although none of the structures found are thermodynamically stable, and none are expected to remain superconducting above 17 K at 10 kbar, a number of metallic compounds with fcc Lu lattices -- as suggested by the experimental X-ray diffraction measurements of the majority phase -- are identified. The system whose calculated equation of states matches best with that measured for the majority phase is fluorite-type LuH2, whose 10 kbar superconducting critical temperature was estimated to be 0.09 K using the Allen-Dynes modified McMillan equation. △ Less

Submitted 27 March, 2023; originally announced March 2023.

Comments: 11 pages, 8 figures

Intercalating Helium into A-site Vacant Perovskites

Authors: Stefano Racioppi, Maosheng Miao, Eva Zurek

Abstract: Evolutionary searches were employed to predict the most stable structures of perovskites with helium atoms on their A-sites up to pressures of 10 GPa. The thermodynamics associated with helium intercalation into [CaZr]F6, structure that [He]2[CaZr]F6 adopts under pressure, and the mechanical properties of the parent perovskite and helium-bearing phase were studied via density functional theory (DF… ▽ More Evolutionary searches were employed to predict the most stable structures of perovskites with helium atoms on their A-sites up to pressures of 10 GPa. The thermodynamics associated with helium intercalation into [CaZr]F6, structure that [He]2[CaZr]F6 adopts under pressure, and the mechanical properties of the parent perovskite and helium-bearing phase were studied via density functional theory (DFT) calculations. The pressure-temperature conditions where the formation of HeAlF3, HeGaF3, HeInF3, HeScF3 and HeReO3 from elemental helium and the vacant A-site perovskites is favored were found. Our DFT calculations show that entropy can stabilize the helium-filled perovskites provided that the volume that the noble gas atom occupies within their pores is larger than within the elemental solid at that pressure. We find that helium incorporation will increase the bulk modulus of AlF3 from a value characteristic of tin to one characteristic of steel, and hinders rotations of its octahedra that occur under pressure. △ Less

Submitted 21 March, 2023; originally announced March 2023.

Crystal Chemistry at High Pressure

Authors: Katerina P. Hilleke, Eva Zurek

Abstract: An overview of the behavior of materials at high pressure is presented, starting from the effects on single atoms driving electronic transitions and changes in periodic trends. A range of high-pressure-induced phenomena in the solid state are then discussed building on the atomic changes, including bizarre electronic structures, electrides, compounds of noble gases, changes in elemental miscibilit… ▽ More An overview of the behavior of materials at high pressure is presented, starting from the effects on single atoms driving electronic transitions and changes in periodic trends. A range of high-pressure-induced phenomena in the solid state are then discussed building on the atomic changes, including bizarre electronic structures, electrides, compounds of noble gases, changes in elemental miscibility, and strange structural and bonding configurations. In the final section, the field of high pressure superconductivity is discussed, as high pressure phases have generated immense study and excitement as some of their critical superconducting temperatures approach room temperature. △ Less

Submitted 3 January, 2023; originally announced January 2023.

Comments: Written for Comprehensive Inorganic Chemistry III (2023)

Conventional high-temperature superconductivity in metallic, covalently bonded, binary-guest C-B clathrates

Authors: Nisha Geng, Katerina P. Hilleke, Li Zhu, Xiaoyu Wang, Timothy A. Strobel, Eva Zurek

Abstract: Inspired by the synthesis of XB3C3 (X= Sr, La) compounds in the bipartite sodalite clathrate structure, density functional theory (DFT) calculations are performed on members of this family containing up to two different metal atoms. A DFT-chemical pressure analysis on systems with X= Mg, Ca, Sr, Ba reveals that the size of the metal cation, which can be tuned to stabilize the B-C framework, is key… ▽ More Inspired by the synthesis of XB3C3 (X= Sr, La) compounds in the bipartite sodalite clathrate structure, density functional theory (DFT) calculations are performed on members of this family containing up to two different metal atoms. A DFT-chemical pressure analysis on systems with X= Mg, Ca, Sr, Ba reveals that the size of the metal cation, which can be tuned to stabilize the B-C framework, is key for their ambient-pressure dynamic stability. High-throughput density functional theory calculations on 105 Pm-3 symmetry XYB6C6 binary-guest compounds (where X, Y are electropositive metal atoms) find 22 that are dynamically stable at 1 atmosphere, expanding the number of potentially synthesizable phases by 19 (18 metals and 1 insulator). The density of states at the Fermi level and superconducting critical temperature, Tc, can be tuned by changing the average oxidation state of the metal atoms, with Tc being highest for an average valence of +1.5. KPbB6C6, with an ambient-pressure Eliashberg Tc of 88 K, is predicted to possess the highest-Tc among the studied Pm-3n XB3C3 or Pm-3 XY B6C6 phases, and calculations suggest it may be synthesized using high-pressure high-temperature techniques then quenched to ambient conditions. △ Less

Submitted 1 December, 2022; v1 submitted 10 October, 2022; originally announced October 2022.

aflow++: a C++ framework for autonomous materials design

Authors: C. Oses, M. Esters, D. Hicks, S. Divilov, H. Eckert, R. Friedrich, M. J. Mehl, A. Smolyanyuk, X. Campilongo, A. van de Walle, J Schroers, A. G. Kusne, I. Takeuchi, E. Zurek, M. Buongiorno Nardelli, M. Fornari, Y. Lederer, O. Levy, C. Toher, S. Curtarolo

Abstract: The realization of novel technological opportunities given by computational and autonomous materials design requires efficient and effective frameworks. For more than two decades, aflow++ (Automatic-Flow Framework for Materials Discovery) has provided an interconnected collection of algorithms and workflows to address this challenge. This article contains an overview of the software and some of it… ▽ More The realization of novel technological opportunities given by computational and autonomous materials design requires efficient and effective frameworks. For more than two decades, aflow++ (Automatic-Flow Framework for Materials Discovery) has provided an interconnected collection of algorithms and workflows to address this challenge. This article contains an overview of the software and some of its most heavily-used functionalities, including algorithmic details, standards, and examples. Key thrusts are highlighted: the calculation of structural, electronic, thermodynamic, and thermomechanical properties in addition to the modeling of complex materials, such as high-entropy ceramics and bulk metallic glasses. The aflow++ software prioritizes interoperability, minimizing the number of independent parameters and tolerances. It ensures consistency of results across property sets - facilitating machine learning studies. The software also features various validation schemes, offering real-time quality assurance for data generated in a high-throughput fashion. Altogether, these considerations contribute to the development of large and reliable materials databases that can ultimately deliver future materials systems △ Less

Submitted 5 August, 2022; originally announced August 2022.

Comments: 47 pages, 14 figures

Rational Design of Superconducting Metal Hydrides via Chemical Pressure Tuning

Authors: Katerina P. Hilleke, Eva Zurek

Abstract: The high critical superconducting temperatures ($T_c$s) of metal hydride phases with clathrate-like hydrogen networks have generated great interest. Herein, we employ the Density Functional Theory-Chemical Pressure (DFT-CP) method to explain why certain electropositive elements adopt these structure types, whereas others distort the hydrogenic lattice, thereby decreasing the $T_c$. The progressive… ▽ More The high critical superconducting temperatures ($T_c$s) of metal hydride phases with clathrate-like hydrogen networks have generated great interest. Herein, we employ the Density Functional Theory-Chemical Pressure (DFT-CP) method to explain why certain electropositive elements adopt these structure types, whereas others distort the hydrogenic lattice, thereby decreasing the $T_c$. The progressive opening of the H$_{24}$ polyhedra in MH$_6$ phases is shown to arise from internal pressures exerted by large metal atoms, some of which may favor an even higher hydrogen content that loosens the metal atom coordination environments. The stability of the LaH$_{10}$ and LaBH$_8$ phases is tied to stuffing of their shared hydrogen network with either additional hydrogen or boron atoms. The predictive capabilities of DFT-CP are finally applied to the Y-X-H system to identify possible ternary additions yielding a superconducting phase stable to low pressures. △ Less

Submitted 23 May, 2022; originally announced May 2022.

Comments: 13 pages, 3 figures

Topological Electride Phase of Sodium at High Pressures and Temperatures

Authors: Busheng Wang, Katerina P. Hilleke, Xiaoyu Wang, Danae N. Polsin, Eva Zurek

Abstract: Ab initio evolutionary structure searches coupled with quasiharmonic calculations predict that the insulating Na hP4 phase transitions to a novel P63/m phase between 200 GPa at 150 K, and 350 GPa at 1900 K. P63/m Na is a topological semimetal with a Dirac nodal surface that is protected by a non-symmorphic symmetry, S2z . It is characterized by localized non-nuclear charge within 1D honeycomb chan… ▽ More Ab initio evolutionary structure searches coupled with quasiharmonic calculations predict that the insulating Na hP4 phase transitions to a novel P63/m phase between 200 GPa at 150 K, and 350 GPa at 1900 K. P63/m Na is a topological semimetal with a Dirac nodal surface that is protected by a non-symmorphic symmetry, S2z . It is characterized by localized non-nuclear charge within 1D honeycomb channels and 0D cages rendering it an electride. These results highlight the complexity of warm dense sodiums electronic structure and free energy landscape that emerges at conditions where ionic cores overlap. △ Less

Submitted 12 May, 2022; originally announced May 2022.

The Microscopic Diamond Anvil Cell: Stabilization of Superhard, Superconducting Carbon Allotropes at Ambient Pressure

Authors: Xiaoyu Wang, Davide M Proserpio, Corey Oses, Cormac Toher, Stefano Curtarolo, Eva Zurek

Abstract: A metallic covalently bonded carbon allotrope is predicted via first principles calculations. It is composed of an $sp^3$ carbon framework that acts as a diamond anvil cell by constraining the distance between parallel cis-polyacetylene chains. The distance between these $sp^2$ carbon atoms renders the phase metallic, and yields two well-nested nearly parallel bands that span the Fermi level. Calc… ▽ More A metallic covalently bonded carbon allotrope is predicted via first principles calculations. It is composed of an $sp^3$ carbon framework that acts as a diamond anvil cell by constraining the distance between parallel cis-polyacetylene chains. The distance between these $sp^2$ carbon atoms renders the phase metallic, and yields two well-nested nearly parallel bands that span the Fermi level. Calculations show that this phase is a conventional superconductor, with the motions of the $sp^2$ carbons being key contributors to the electron phonon coupling. The $sp^3$ carbon atoms impart superior mechanical properties, with a predicted Vickers hardness of 48~GPa. This phase, metastable at ambient conditions, could be made via cold compression of graphite to 40~GPa. A family of multifunctional materials with tunable superconducting and mechanical properties could be derived from this phase by varying the $sp^2$ versus $sp^3$ carbon content and by doping. △ Less

Submitted 7 April, 2022; originally announced April 2022.

Structural Diversity and Superconductivity in S-P-H Ternary Hydrides Under Pressure

Authors: Nisha Geng, Tiange Bi, Eva Zurek

Abstract: Evolutionary structure searches revealed a plethora of stable and low-enthalpy metastable phases in the S-P-H ternary phase diagram under pressure. A wide variety of crystalline structure types were uncovered ranging from those possessing one-dimensional chains, two-dimensional sheets based on S-H or S-P-H square lattices as well as S-H or P-H honeycombs, and cage-like structures. Some of the cage… ▽ More Evolutionary structure searches revealed a plethora of stable and low-enthalpy metastable phases in the S-P-H ternary phase diagram under pressure. A wide variety of crystalline structure types were uncovered ranging from those possessing one-dimensional chains, two-dimensional sheets based on S-H or S-P-H square lattices as well as S-H or P-H honeycombs, and cage-like structures. Some of the cage-like structures could be derived from doping the high-pressure high-temperature superconducting $Im\bar{3}m$ H$_3$S phase with phosphorous. Most of the discovered compounds were metallic, however those derived from $Im\bar{3}m$ H$_3$S lattices with low levels of P-doping were predicted to possess the highest superconducting critical temperatures ($T_c$s). The propensity for phosphorous to assume octahedral coordination, as well as the similar radii of sulfur and phosphorous are key to maintaining a high density of states at the Fermi level in $Im\bar{3}m$ S$_{0.875}$P$_{0.125}$H$_3$, whose $T_c$ was estimated to be similar to that of H$_3$S at 200~GPa. △ Less

Submitted 1 January, 2022; originally announced January 2022.

Materials under high pressure: A chemical perspective

Authors: Katerina P. Hilleke, Tiange Bi, Eva Zurek

Abstract: At high pressure, the typical behavior of elements dictated by the periodic table - including oxidation numbers, stoichiometries in compounds, and reactivity, to name but a few - is altered dramatically. As pressure is applied, the energetic ordering of atomic orbitals shifts, allowing core orbitals to become chemically active, atypical electron configurations to occur, and in some cases, non-atom… ▽ More At high pressure, the typical behavior of elements dictated by the periodic table - including oxidation numbers, stoichiometries in compounds, and reactivity, to name but a few - is altered dramatically. As pressure is applied, the energetic ordering of atomic orbitals shifts, allowing core orbitals to become chemically active, atypical electron configurations to occur, and in some cases, non-atom-centered orbitals to form in the interstices of solid structures. Strange stoichiometries, structures, and bonding motifs result. Crystal structure prediction tools, not burdened by preconceived notions about structural chemistry learned at atmospheric pressure, have been applied to great success to explore phase diagrams at high pressure, identifying novel structures in diverse chemical systems. Several of these have been subsequently observed by experimental investigations, whose access to high-pressure regimes is bolstered by advances in diamond anvil cell and dynamic compression techniques. The joint efforts of experiment and theory have led to particular success in the realm of high-temperature superconductors, identifying many novel phases whose superconducting transition approaches room temperature. △ Less

Submitted 30 December, 2021; originally announced December 2021.

Comments: 17 pages (35 with references), 6 figures

Nature of the bonded-to-atomic transition in liquid silica to TPa pressures

Authors: Shuai Zhang, Miguel A. Morales, Raymond Jeanloz, Marius Millot, S. X. Hu, Eva Zurek

Abstract: First-principles calculations and analysis of the thermodynamic, structural, and electronic properties of liquid SiO$_2$ characterize the bonded-to-atomic transition at 0.1--1.6 TPa and 10$^4$--10$^5$ K (1--7 eV), the high-energy-density regime relevant to understanding planetary interiors. We find strong ionic bonds that become short-lived due to high kinetics during the transition, with sensitiv… ▽ More First-principles calculations and analysis of the thermodynamic, structural, and electronic properties of liquid SiO$_2$ characterize the bonded-to-atomic transition at 0.1--1.6 TPa and 10$^4$--10$^5$ K (1--7 eV), the high-energy-density regime relevant to understanding planetary interiors. We find strong ionic bonds that become short-lived due to high kinetics during the transition, with sensitivity of the transition temperature to pressure, and our calculated Hugoniots agree with past experimental data. These results reconcile previous experimental and theoretical findings by clarifying the nature of the bond dissociation process in early Earth and "rocky" (oxide) constituents of large planets. △ Less

Submitted 8 December, 2021; originally announced December 2021.

Comments: 11 pages, 11 figures

Tuning Chemical Precompression: Theoretical Design and Crystal Chemistry of Novel Hydrides in the Quest for Warm and Light Superconductivity at Ambient Pressures

Authors: Katerina P. Hilleke, Eva Zurek

Abstract: Over the past decade, a combination of crystal structure prediction techniques and experimental synthetic work has thoroughly explored the phase diagrams of binary hydrides under pressure. The fruitfulness of this dual approach is demonstrated in the recent identification of several superconducting hydrides with $T_c$s approaching room temperature. We start with an overview of the computational pr… ▽ More Over the past decade, a combination of crystal structure prediction techniques and experimental synthetic work has thoroughly explored the phase diagrams of binary hydrides under pressure. The fruitfulness of this dual approach is demonstrated in the recent identification of several superconducting hydrides with $T_c$s approaching room temperature. We start with an overview of the computational procedures for predicting stable structures and estimating their propensity for superconductivity. A survey of phases with high $T_c$ reveals some common structural features that appear conducive to the strong coupling of the electronic structure with atomic vibrations that leads to superconductivity. We discuss the stability and superconducting properties of phases containing two of these -- molecular H$_2$ units mixed with atomic H and hydrogenic clathrate-like cages -- as well as more unique motifs. Finally, we argue that ternary hydride phases, which are far less-explored, are a promising route to achieving simultaneously superconductivity at high temperatures and stability at low pressures. Several ternary hydrides arise from the addition of a third element to a known binary hydride structure through site mixing or onto a new site -- and several more are based on altogether new structural motifs. △ Less

Submitted 5 November, 2021; originally announced November 2021.

Comments: 19 pages, 4 tables, 5 figures

A Little Bit of Carbon Can do a Lot for Superconductivity in H$_3$S

Authors: Xiaoyu Wang, Tiange Bi, Katerina P. Hilleke, Anmol Lamichhane, Russell J. Hemley, Eva Zurek

Abstract: First-principles calculations were carried out to provide a chemical basis for proposed structures associated with the recently reported room-temperature superconductivity in a carbonaceous sulfur hydride material under pressure. Calculations were performed on supercells of H$_3$S doped with 1.85-25\% carbon, corresponding to SH$_3$~$\rightarrow$~CH$_3$ or SH$_3$~$\rightarrow$~CH$_4$ substitutions… ▽ More First-principles calculations were carried out to provide a chemical basis for proposed structures associated with the recently reported room-temperature superconductivity in a carbonaceous sulfur hydride material under pressure. Calculations were performed on supercells of H$_3$S doped with 1.85-25\% carbon, corresponding to SH$_3$~$\rightarrow$~CH$_3$ or SH$_3$~$\rightarrow$~CH$_4$ substitutions, primarily at pressures of 270 GPa where the maximum critical temperature, $T_c$, has been reported. In the first type of substitution, the carbon atoms can be six-fold coordinated, stabilizing a CH$_6$ configuration within the cubic H$_3$S framework structure that forms under pressure. In the second, the carbon can be four-fold coordinated as methane intercalated into the H-S lattice, with or without an additional hydrogen in the framework. The results indicate that unusual local bonding configurations with respect to carbon can be stabilized under pressure. The doping breaks degenerate bands, lowering the density of states at the Fermi level ($N_F$), and localizing electrons in C-H bonds. Low levels of CH$_4$ doping do not increase $N_F$ to values as high as those calculated for $Im\bar{3}m$ H$_3$S, but they do result in a larger logarithmic average phonon frequency, and an electron-phonon coupling parameter comparable to that of $R3m$ H$_3$S. The $T_c$s estimated for carbon doping levels ranging from 1.85-5.7\% are compatible with experimental measurements for the C-S-H superconductor. △ Less

Submitted 14 November, 2021; v1 submitted 20 September, 2021; originally announced September 2021.

Structural Motifs and Bonding in Two Families of Boron Structures Predicted at Megabar Pressures

Authors: Katerina P. Hilleke, Eva Zurek, Tadashi Ogitsu, Shuai Zhang

Abstract: The complex crystal chemistry of elemental boron has led to numerous proposed structures with distinctive motifs as well as contradictory findings. Herein, evolutionary structure searches performed at 100 GPa have uncovered a series of potential new metastable phases of boron, and bonding analyses were carried out to elucidate their electronic structure. These polymorphs, dynamically stable at 100… ▽ More The complex crystal chemistry of elemental boron has led to numerous proposed structures with distinctive motifs as well as contradictory findings. Herein, evolutionary structure searches performed at 100 GPa have uncovered a series of potential new metastable phases of boron, and bonding analyses were carried out to elucidate their electronic structure. These polymorphs, dynamically stable at 100 GPa, were grouped into two families. The first was derived from the thermodynamic minimum at these conditions, $α$-Ga, whereas channels comprised the second. Two additional intergrowth structures were uncovered, and it was shown they could be constructed by stacking layers of $α$-Ga-like and channel-like allotropes on top of each other. A detailed bonding analysis revealed networks of four-center $σ$-bonding functions linked by two-center B-B bonds in the $α$-Ga based structures, and networks that were largely composed of three-center $σ$-bonding functions in the channel-based structures. Seven of these high pressure phases were found to be metastable at atmospheric conditions, and their Vickers hardnesses were estimated to be $\sim$36 GPa. △ Less

Submitted 1 January, 2021; originally announced January 2021.

Comments: 14 pages, 12 figures, 3 tables

Journal ref: Phys. Rev. Materials 5, 053605 (2021)

The Li-F-H Ternary System at High Pressures

Authors: Tiange Bi, Andrew Shamp, Tyson Terpstra, Russell J. Hemley, Eva Zurek

Abstract: Evolutionary crystal structure prediction searches have been employed to explore the ternary Li-F-H system at 300 GPa. Metastable phases were uncovered within the static lattice approximation, with LiF$_3$H$_2$, LiF$_2$H, Li$_3$F$_4$H, LiF$_4$H$_4$, Li$_2$F$_3$H and LiF$_3$H lying within 50 meV/atom of the 0 K convex hull. All of these phases contain H$_n$F$_{n+1}^-$ ($n$ = 1; 2) anions, and Li… ▽ More Evolutionary crystal structure prediction searches have been employed to explore the ternary Li-F-H system at 300 GPa. Metastable phases were uncovered within the static lattice approximation, with LiF$_3$H$_2$, LiF$_2$H, Li$_3$F$_4$H, LiF$_4$H$_4$, Li$_2$F$_3$H and LiF$_3$H lying within 50 meV/atom of the 0 K convex hull. All of these phases contain H$_n$F$_{n+1}^-$ ($n$ = 1; 2) anions, and Li$^+$ cations. Other structural motifs such as LiF slabs, H$_3^+$ molecules, and F$^{δ-}$ ions are present in some of the low enthalpy Li-F-H structures. The bonding within the H$_n$F$_{n+1}^-$ molecules, which may be bent or linear, symmetric or asymmetric, is analyzed. The five phases closest to the hull are insulators, while LiF$_3$H is metallic and predicted to have a vanishingly small superconducting critical temperature. This study lays the foundation for future investigations of the role of temperature and anharmonicity on the stability and properties of compounds and alloys in the Li-F-H ternary system. △ Less

Submitted 30 December, 2020; originally announced December 2020.

Comments: 11 pages, 4 figures, 1 table

A Metastable CaSH$_3$ Phase Composed of HS Honeycomb Sheets that is Superconducting Under Pressure

Authors: Yan Yan, Tiange Bi, Nisha Geng, Xiaoyu Wang, Eva Zurek

Abstract: Evolutionary searches predicted a number of ternary phases that could be synthesized at pressures of 100-300~GPa. $P6_3/mmc$ CaSH$_2$, $Pnma$ CaSH$_2$, $Cmc2_1$ CaSH$_6$, and $I\bar{4}$ CaSH$_{20}$ were composed of a Ca-S lattice along with H$_2$ molecules coordinated in a ``side-on'' fashion to Ca. The H-H bond lengths in these semiconducting phases were elongated because of H$_2$ $σ\rightarrow$… ▽ More Evolutionary searches predicted a number of ternary phases that could be synthesized at pressures of 100-300~GPa. $P6_3/mmc$ CaSH$_2$, $Pnma$ CaSH$_2$, $Cmc2_1$ CaSH$_6$, and $I\bar{4}$ CaSH$_{20}$ were composed of a Ca-S lattice along with H$_2$ molecules coordinated in a ``side-on'' fashion to Ca. The H-H bond lengths in these semiconducting phases were elongated because of H$_2$ $σ\rightarrow$ Ca d donation, and Ca d$\rightarrow$ H$_2$ $σ^*$ back-donation, via a Kubas-like mechanism. $P\bar{6}m2$ CaSH$_3$, consisting of two-dimensional HS and CaH$_2$ sheets, was metastable and metallic above \edit{128~GPa}. The presence of van Hove singularities increased its density of states at the Fermi level, and concomitantly the superconducting critical temperature, which was estimated to be as high as \edit{$\sim$100~K at 128~GPa}. This work will inspire the search for superconductivity in materials based upon \edit{honeycomb HX (X=S, Se, Te), and MH$_2$ (M=Mg, Ca, Sr, Ba) layers} under pressure. △ Less

Submitted 29 December, 2020; originally announced December 2020.

Superconductivity to 262 kelvin via catalyzed hydrogenation of yttrium at high pressures

Authors: Elliot Snider, Nathan Dasenbrock-Gammon, Raymond McBride, Xiaoyu Wang, Noah Meyers, Keith V. Lawler, Eva Zurek, Ashkan Salamat, Ranga Dias

Abstract: Room temperature superconductivity has been achieved under high pressure in an organically derived carbonaceous sulfur hydride with a critical superconducting transition temperature (Tc) of 288 kelvin. This development is part of a new class of dense, hydrogen rich materials with remarkably high critical temperatures. Metal superhydrides are a subclass of these materials that provide a different a… ▽ More Room temperature superconductivity has been achieved under high pressure in an organically derived carbonaceous sulfur hydride with a critical superconducting transition temperature (Tc) of 288 kelvin. This development is part of a new class of dense, hydrogen rich materials with remarkably high critical temperatures. Metal superhydrides are a subclass of these materials that provide a different and potentially more promising route to very high Tc superconductivity. The most promising binary metal superhydrides contain alkaline or rare earth elements, and recent experimental observations of LaH10 have shown them capable of Tc s up to 250 to 260 kelvin. Predictions have shown yttrium superhydrides to be the most promising with an estimated Tc in excess of 300 kelvin for YH10. Here we report the synthesis of an yttrium superhydride that exhibits superconductivity at a critical temperature of 262 kelvin at 182 gigapascal. A palladium thin film assists the synthesis by protecting the sputtered yttrium from oxidation and promoting subsequent hydrogenation. Phonon mediated superconductivity is established by the observation of zero resistance, an isotope effect and the reduction of Tc under an external magnetic field. The upper critical magnetic field is 103 tesla at zero temperature. We suggest YH9 is the synthesized product based on comparison of the measured Raman spectra and Tc to calculated Raman results. △ Less

Submitted 25 December, 2020; originally announced December 2020.

Journal ref: Phys. Rev. Lett. 126, 117003 (2021)

Fluorides of silver under large compression

Authors: Dominik Kurzydłowski, Mariana Derzsi, Eva Zurek, Wojciech Grochala

Abstract: The silver-fluorine phase diagram has been scrutinized as a function of external pressure using theoretical methods. Our results indicate that two novel stoichiometries containing Ag+ and Ag2+ cations (Ag3F4 and Ag2F3) are thermodynamically stable at ambient and low pressure. Both are computed to be magnetic semiconductors at ambient pressure conditions. For Ag2F5, containing both Ag2+ and Ag3+, w… ▽ More The silver-fluorine phase diagram has been scrutinized as a function of external pressure using theoretical methods. Our results indicate that two novel stoichiometries containing Ag+ and Ag2+ cations (Ag3F4 and Ag2F3) are thermodynamically stable at ambient and low pressure. Both are computed to be magnetic semiconductors at ambient pressure conditions. For Ag2F5, containing both Ag2+ and Ag3+, we find that strong 1D antiferromagnetic coupling is retained throughout the pressure-induced phase transition sequence up to 65 GPa. Our calculations show that throughout the entire pressure range of their stability the mixed valence fluorides preserve a finite band gap at the Fermi level. We also confirm the possibility of synthesizing AgF4 as a paramagnetic compound at high pressure. Our results indicate that this compound is metallic in its thermodynamic stability region. Finally, we present general considerations on the thermodynamic stability of mixed valence compounds of silver at high pressure. △ Less

Submitted 17 December, 2020; originally announced December 2020.

Journal ref: Chemistry - A European Journal 2021

Predicting Superhard Materials via a Machine Learning Informed Evolutionary Structure Search

Authors: Patrick Avery, Xiaoyu Wang, Davide M. Proserpio, Cormac Toher, Corey Oses, Eric Gossett, Stefano Curtarolo, Eva Zurek

Abstract: Good agreement was found between experimental Vickers hardnesses, $H_\text{v}$, of a wide range of materials and those calculated by three macroscopic hardness models that employ the shear and/or bulk moduli obtained from: (i) first principles via AFLOW-AEL (AFLOW Automatic Elastic Library), and (ii) a machine learning (ML) model trained on materials within the AFLOW repository. Because… ▽ More Good agreement was found between experimental Vickers hardnesses, $H_\text{v}$, of a wide range of materials and those calculated by three macroscopic hardness models that employ the shear and/or bulk moduli obtained from: (i) first principles via AFLOW-AEL (AFLOW Automatic Elastic Library), and (ii) a machine learning (ML) model trained on materials within the AFLOW repository. Because $H_\text{v}^\text{ML} $ values can be quickly estimated, they can be used in conjunction with an evolutionary search to predict stable, superhard materials. This methodology is implemented in the XtalOpt evolutionary algorithm. Each crystal is minimized to the nearest local minimum, and its Vickers hardness is computed via a linear relationship with the shear modulus discovered by Teter. Both the energy/enthalpy and $H_\text{v, Teter}^{\text{ML}}$ are employed to determine a structure's fitness. This implementation is applied towards the carbon system, and 43 new superhard phases are found. A topological analysis reveals that phases estimated to be slightly harder than diamond contain a substantial fraction of diamond and/or lonsdaleite. △ Less

Submitted 13 June, 2019; originally announced June 2019.